Terminally halogenated olefinic compounds



United States Patent 3,225,106 TERMINALLY HALOGENATED OLEFINIC COMPOUNDS Robert Rabinowitz, Stamford, Conn., assignor to American Cyanamid Company, New York, N.Y., a corporation of Maine No Drawing. Filed Jan. 15, 1962, Ser. No. 166,412

7 Claims. (Cl. 260-649) The present invention relates to the preparation of organic compounds having terminally halogenated olefin moieties. More particularly, the instant discovery concerns a simple and straightforward process for preparing these organic compounds according to the following equation:

RI! RI! RSPO rwi=ox x R dX X R in the aboveformulae represents alkyl (C -C substituted and unsubstituted, aryl, substituted and unsubstituted, and cycloalkyl, substituted and unsubstituted; R represents hydrogen, alkyl (C -C C phenyl, naphthyl, cyclohexyl, benzoyl, furfuryl, styrenyl, halo-substituted alkyl (C -C halosubstituted phenyl; R represents hydrogen, alkyl (C C alkenyl (C -C phenyl, naphthyl, cyclohexyl, furfuryl, styrenyl, halo-substituted alkyl (C C halo-substituted phenyl; and R and R" combined may represent the residue of fluorenone, l-indanone, Z-indanone, 1- tetralone, indenone, anthrone and benzanthrone; X represents hydrogen, chlorine, bromine and fluorine and X represents chlorine, bromine and fluorine; X and X each represent chlorine, bromine and iodine.

Pursuant to the present invention a one-step process which is simple, straightforward and very desirable has been found for preparing a large number of organophosphorus compounds containing terminally halogenated olefins and represented by the product formula in the equation, supra.

According to the instant discovery a tertiary phosphine of the formula (A) is brought into reactive contact with a polyhalomethane (B) and a carbonyl compound (C) at a temperature in the range of 25 C. to 200 C., preferably 50 C. to 150 C. Superatmospheric pressure may be employed where it is necessary to contain the more volatile reactants. Generally, however, atmospheric pressure is adequate.

For best results the tertiary phosphine is first admixed with the carbonyl reactant and the resulting mixture contacted with the polyhalomethane compound. Any sequence of addition, however, may be employed.

Typical polyhalomethane reactants within the purview of the present invention are the following: CCL CCl Br, CCl Br CClBr CCigF, CCl F CHCl F, CHBr F, CHBrClF, CHCl Br, CCI H, CHBr CCl I, and the like.

Typical carbonyl reactants useful in the process of the present invention for producing the corresponding products are the following: propionaldehyde, crotonaldehyde, chloral, n-heptaldehyde, furfural, benzaldehyde, mchlorobenzaldehyde, cinnamaldehyde, acetone, methyl vinyl ketone, cyclohexanone, methyl cyclohexyl ketone, acetophenone, benzophenone, methyl ,B-naphthyl ketone, divinyl ketone, dibutyl ketone, didecyl ketone, fiuorenone, chloranil, benzil.

Among the many tertiary phosphine reactants which may be employed for producing the products of the present invention are the following: tributylphosphine, tris(2- alkenyl (C 3,225,106 Patented Dec. 21, 1965 cyanoethyl)phosphine, tricyclohexylphosphine, diethylphenylphosphine, trimethylphosphine, trioctylphosphine, triisobutylphosphine, triisopropylphosphine, diethyl-pbromophenylphosphjne, triphenylphosphine, diethylpropylphosphine, diethyl p methoxyphenylphosphine, trioctadecylphosphine, tridodecylphosphine, and the like.

The reactants of the present invention are usually brought together in stoichiometric amounts, for instance, one mole of the aldehyde reactant with one mole of the tertiary phosphine in the presence of at least one mole of the polyhalomethane reactant. One-half mole of the ketone reactant per mole of the tertiary phosphine is generally employed, at least one mole of the polyhalomethane also being present.

Generally, an excess of the polyhalomethane is employed to provide a solvent medium. Other solvents within the purview of the instant discovery are inert organic solvents, such as aromatic hydrocarbons, cyclic ethers and non-cyclic ethers. Typical solvents are benzene, toluene, dioxane, tetrahydrofuran, methyl ethyl ether, diethyl ether, and the like.

In the case where high temperatures are employed a closed system is used, and autogenous pressure employed. The present invention will best be understood from the following illustrative examples:

EXAMPLE I A mixture of 72 grams triphenylphosphine (0.274 mole) and 29 grams benzaldehyde (0.274 mole) is dissolved in milliliters of carbon tetrachloride. and the resulting mixture heated at 60 C. in a closed system for 2 hours, at which point, gas chromatographic analysis indicates that the reaction is complete. Addition of 200 milliliters of low boiling petroleum ether to the reaction mixture precipitates 69 grams of triphenylphosphine oxide. Fractional distillation of the filtrate gives less than 1 gram of unreacted benzaldehyde, 15.1 grams benzal chloride and 16 grams of [3,fi-dichlorostyrene.

EXAMPLE II A mixture of 2.0 grams triphenylphosphine (0.00765 mole) and 0.92 gram acetophenone (0.00765 mole) is dissolved in 4.0 milliters of carbon tetrachloride. The reaction is complete as determined by gas chromatographic analysis, after 20 minutes at 60 C. followed by 72 hours at room temperature. The product 1,1-dichloro-2-phenylis identified by mass spectroscopy. Recovery accomplished as in Example I, supra, using 25 milliliters of petroleum ether.

EXAMPLE III A mixture of 2.0 grams triphenylphosphine (0.00765 mole) and 0.87 gram benzaldehyde (0.00765 mole) is dissolved in 4 milliliters bromotrichloromethane. In 3 minutes a yellow color appears and heat is evolved. This evolution is controlled by cooling and this is continued for 10 minutes until there is no further heat evolution. The desired @fl-diohlorostyrene product is detected by mass spectroscopy and recovered as in Example I, supra, using only 20 milliliters of petroleum ether.

EXAMPLE IV The resulting 5,5-difiuorostyrene is identified by mass spectroscopy and recovered as in Example I, supra, using only 25 milliliters of petroleum ether.

EXAMPLE V The following are charged into a 100 milliliter stainless steel autoclave: 2.17 grams benzaldehyde (0.023 mole), 5.0 grams triphenylphosphine (0.023 mole), 7 milliliters of benzene, and finally 7.0 grams dichlorodifiuoromethane. This is heated at 110 C.l20 C. for 24 hours and 180 C. for 3 hours. The system is cooled, vented and the dichlorodifiuoromethane allowed to evaporate. The resulting [3,fi-difluorostyrene is identified by vapor phase chromatography and recovered as in Example I, supra, using only 40 milliliters of petroleum ether.

EXAMPLE VI Thirty-two and seven tenths grams (0.125 mole) of triphenylphosphine, 70 milliliters of carbon tetrachloride,

mixed and heated at 60 C. for 4 hours. The reaction mixture which results is first stripped (in vacuo, 22 C.) to remove excess CCl The resulting mixture is then treated with cold ethanol, precipitate removed, and the precipitate treated with ethyl ether to dissolve desired product, 1,1-diphenyldichloroethylene. Ether removed by volatilization to leave crystalline product.

EXAMPLE VII A solution of grams triphenylphosphine (0.057 mole), 5.18 grams 9-fluorenone (0.0285 mole) in 30 milliliters carbon tetrachloride is heated at 65 C. for 6 /2 hours. The solution is then shaken with 25 grams water heated on a steam bath for 15 minutes. The mixture is r extracted with CHCl the extract dried over alumina and the volatiles removed under vacuum. The residue is triturated with ethanol and cooled to 10 C. A total of 6.3 grams of 9-dichloromethylenefluorene is isolated. The filtrate is devolatilized and the residue triturated with ethyl ether at -l5 C. to give 14.5 grams of triphenyland 22.8 grams (0.125 mole) of benzophenone are adphosphine oxide.

Ta le I $1! Exam. R31 OX X X X R C R R C=CX X No. (A) (B) (C) Molar ratio 'Iemp., Solv. (E)

R X X X X A:B:C O.

VIII Tributyl- C1 C1 C1 Cl Pliopiionalde- 5 1 None CHzOHzCfi -"CClz iv e. IX Trieyelohexyl- C1 01 Cl Br Grotonaldehyde. 2 0.5 Benzene... CH3CH=CHCH=OC12 X TrisI(12-1(3yano- 01 Cl Br Br Chloral 3 1 T0luene. CClaCH=CCl2 et y XI DiethylphenyL. Cl Br Br Br n-gegtalde- 5 1 0 None n-C6H13CH=CO1Br y e. XII Trimethyl F C1 C1 C1 Furfural 8 1 75 Di0xane EOflCH=CC1F XIII Trioctyl- F F 01 Cl m-Chlorobenz- 10 1 *200 Benzenem. OH:CF

aldehyde.

XIV Triis0butyln F Br Br Cinnamalde- 2 1 -20 Ethyl -or1=oH-o11:oHF

hyde. ether. XV Triisopropy1- H F Cl Br Acetone 3 0.5 0 Tetrahy- (CH3) O=OHF drofuran.

XVI Diethyl-p- H 01 Cl Br Methyl vinyl 8 0.5 30 None CHZCCH=CH bromophenyl-. ketone.

CHCl

XVII Triphenyl- H C1 C1 C1 Cyclohexanone. 5 0.5 do =CHC1 XVIII Diethylpropy1- H Br Br Br Methylcyclo- 5 0.5 10 do CH3C- hexyl ketono. CHBr (ITCh XIX Diethyl-p-me- 01 c1 c1 c1 Benz0pl1enone 5 0.5 0 do c thoxyphenyl-.

(fiClz XX Tri0ctadeeyl- C1 C1 G1 I Methyl fl-naph- 5 0.5 20 T01uenc OH3C thylkotone.

XXI Tridodecyl- C1 C1 C1 C1 Benzil 5 0.25 10 None Cll-(lll 1 C012 CClz XXII Triphenyl- 01 c1 01 or l indanone 10 05 so do ll CClz #FOOtIlOtB at end of table.

Table I--Continued RI Exam. II I No. RaP CX X X X R CR" R C=GX X (A) B (C) Molarratio Temp., Solv. (E) jRa X X X X AzBzO C.

XXIII... Triphenyl-. F F Br Br 2-indanone -1 1 0.5 10 None XXIV Tris(2cyano- C1 O1 01 Cl lndenone l 10 0.5 75 do ethy1)-.

CC]: I] XXV Diphenyl-p- C1 C1 C1 C1 l-tetralone 1 8 0.5 -do ehlorophenyl.

II XXVI Triphenyl- Cl 01 C1 C1 Anthrone l 12 0.5 60 do XXVII..- Triphenyl- F F Br Br Benzanthronetn 1 10 (15 60 do I H CF:

*Olosed system under autogenous pressure.

Compounds of the present invention may be copolymatoms, substituted alkyl having from 1 to 18 carbon atoms,

erized with vinyl acetate, acrylonitrile, styrene, and the like, to give thermoplastic polymers manifesting flame resistant properties. In addition, compounds of the present invention are useful as insecticides, e.g. against housefiies, mosquito larvae, and the like.

Clearly, the instant discovery encompasses numerous modifications within the skill of the art. Consequently, while the present invention has been described in detail with respect to specific embodiments thereof, it is not intended that these details be construed as limitations upon the scope of the invention, except insofar as they appear in the appended claims.

I claim: 1. A method for the production of compounds of the formula R=CX1X which comprises reacting together as sole reactants a tertiary phosphine of the formula R P, a polyhalomethane of the formula CX X X X and a carbonyl compound of the formula group consisting of alkyl having from 1 to 18 carbon aryl, substituted aryl, and cycloalkyl, said substituents for alkyl and aryl being selected from the group consisting of cyano, lower alkoxy and halo; R represents a member selected from the group consisting of hydrogen, alkyl having from 1 to 12 carbon atoms, alkenyl having from 1 to 12 carbon atoms, phenyl, naphtlhyl, cyclohexyl, benzoyl, furfuryl, styrenyl, halo-substituted alkyl having 1 to 12 carbon atoms, and halo-substituted phenyl; R" represents a member selected from the group consisting of hydrogen, alkyl having from 1 to 12 carbon atoms, alkenyl having from 1 to 12 carbon atoms, phenyl, naphthyl, cyclohexyl, furfuryl, styrenyl, halo-substituted alkyl having from 1 to 12 carbon atoms, and halo-substituted phenyl, and R and R" combined represent the residue of a member of the group consisting of fluorenone, l-indanone, Z-indanone, l-tetralone, indenone, anthrone, and benzanthrone; X represents a member selected from the group consisting of hydrogen, chlorine, bromine and fluorine, and X represents a member selected from the group consisting of chlorine, bromine and fluorine; and X and X each represent a member selected from the group consisting of chlorine, bromine and iodine.

2. The process of claim 1 wherein the temperature is in the range of 50 C. to C.

3. The process of claim 1 wherein the reactants are triphenylphosphine, carbon tetrachloride and benzaldehyde and the product is 8,,8-dichlorostyrene.

4. The process of claim 1 wherein the reactants are triphenylphosphine, carbon tetrachloride and acetophenone and the product is 1,1-dichloro-2-phenyl-propene-1.

7 8 5. The process of claim 1 wherein the reactants are References Cited by the Examiner triphenylphosphine, dibromodifluoromethane and benzal- UNITED STATES PATENTS dehyde and the product is 5,;3-difluorostyrene.

6. The process of claim 1 wherein the reactants are 3O95455 6/1963 Marco et triphenylphosphine, carbon tetrachloride and benzophe- 5 OTHER REFERENCES none and the product is 1,1-diphenyldichloroethylene. t 1 A ch as l 82 1260 7. The process of claim 1 wherein the reactants are 358?? e a em.

triphenylphosphine, carbon tetrachloride and 9-fiuorenone and the product is 9-dichloromethylenefiuorene. LEON ZITVER, Primary Examiner. 

